Detergent compositions exhibiting reduced skin irritation and method of reducing detergent irritation

ABSTRACT

Reduction of skin irritation caused by skin irritating detergent or detergent composition is achieved by incorporating in the irritating detergent or detergent composition an effective amount of a protective agent of the formula   WHERE R is the carboxyl free residue of an aromatic, cycloaliphatic or aralkyl di-, tri- or tetra-carboxylic acid or the carboxyl free residue of the unsaturated polycarboxylic acid product of the polymerization of two to four molecules of a monomeric ethylenically unsaturated C12 to C26 fatty acid or the hydrogenated derivative of said unsaturated polycarboxylic acid product; R&#39;&#39; is hydrogen, hydroxyl, C1-C6-alkyl, or C1-C6-alkyl substituted with hydroxyl or amino; R&#39;&#39;&#39;&#39; and R&#39;&#39;&#39;&#39;&#39;&#39; are hydrogen or C1-C6-alkyl; M IS 0, 1 OR 2; N IS 1, 2, 3 OR 4; N + M IS 2, 3 OR 4; X is oxygen or nitrogen; M is H or a cation; Q IS 0 WHEN X is oxygen and q is 1 when X is nitrogen.

United States Patent [191 Rieder 11] 3,846,554 1 NOV. 5, 1974 DETERGENT COMPOSITIONS EXIIIBITING REDUCED SKIN IRRITATION AND METHOD OF REDUCING DETERGENT IRRITATION [75] Inventor: Walter E. Rieder, Terrace Park,

Ohio

[73] Assignee: Cincinnati Milaeron Inc.,

Cincinnati, Ohio [22] Filed: Dec. 15, 1972 [21] Appl. No.: 315,285

52 us. C1. 424/272, 424/273 [51] Int. Cl A61k 27/00 [58] Field of Search 424/272, 273

[56] References Cited UNITED STATES PATENTS 2,889,332 6/1959 Hughes 260/3096 2,987,522 6/1961 Shen 260/3096 3,251,852 5/1966 De Goote 260/3096 3,354,175 11/1967 Fruhstorfer et al 424/273 FOREIGN PATENTS OR APPLICATIONS 639,398 4/1962 Canada 424/325 1,196,028 6/1970 Great Britain 424/273 OTHER PUBLICATIONS Japanese Appls. JA67012518, R18; 1-3-67; JA 12518, 1/3/67; 29199/69; 42425-JA 7017316.

Primary Examiner-Albert T. Meyers Assistant Examiner,-Frederick E. Waddell Attorney, Agent, or Firm-Pltimley & Tyner [57] ABSTRACT Reduction of skin irritation caused by skin irritating detergent or detergent composition is achieved by incorporating in the irritating detergent or detergent composition'an effective amount of a protective agent of the formula where R is the carboxyl free residue of an aromatic, cycloaliphatic or aralkyl di-, trior tetra-carboxylic acid or the carboxyl free residue of the unsaturated polycarboxylic acid product of the polymerization of two to four molecules of a monomeric ethylenically unsaturated C to C fatty acid or the hydrogenated derivative of said unsaturated polycarboxylic acid product;

R is hydrogen, hydroxyl, C C -alkyl, or C -C alkyl substituted with hydroxyl or amino;

R" and R are hydrogen or C C -a1kyl;

m is 0, 1 or 2;

nis1,2,3or4;

X is oxygen or nitrogen;

M is H or a cation;

q is 0 when X is oxygen and q is 1 when X is nitrogen.

24 Claims, N0 Drawings DETERGENT COMPOSITIONS EXHIBITING REDUCED SKIN IRRITATION AND METHOD OF REDUCING DETERGENT IRRITATION BACKGROUND OF THE INVENTION The present invention relates to protective agents which prevent or reduce skin irritation, particularly to improved detergent compositions which exhibit reduced skin irritation by virtue of the presence of such protective agents, and to methods for preventing or reducing skin irritation resulting from contact with irritating detergent compositions.

Among the most common types of skin irritation are those which can be traced to contact of the skin with a chemical composition containing a detergent. This kind of irritation is believed to be due, in part, to the nature of the detergent itself and, in part, due to the action of the detergent in weakening the resistance of the skin. Most detergents intrinsically irritate the skin, although the degree of irritation will vary significantly with the detergent. Such irritation can result when the skin is contacted with an aqueous solution of such detergent or when such detergent is retained by a fabric on washing with such detergent and the fabric then comes into contact with the skin. Because many otherwise useful detergents are skin irritants they are excluded from applications where the detergent comes into contact with the skin. In some detergent compositions, such as dishwashing liquids and shampoos, a certain degree of skin irritation can be tolerated and is accepted, although not desirable.

The cause of this irritation is not clearly understood, but it is believed that detergents have a denaturing effect on the keratin layer of the skin. As a result, other chemicals which are normally non-irritating and which are commonly combined with detergents, can penetrate the skin and cause irritation. Accordingly, considerable effort has been made to develop agents .which reduce or eliminate not only skin irritation caused by detergents, but skin irritation caused by detergents containing common additives.

It is, therefore, an object of the present invention to prevent or reduce skin irritation resulting from contact of the skin with chemical compositions, particularly detergent compositions.

It is another object of the present invention to provide improved detergent compositions containing a protective agent which prevents or reduces skin irritation which would otherwise result from skin contact with such detergent compositions lacking the protective agent.

Other objects will become apparent from the following description and claims.

DESCRIPTION OF THE INVENTION Prevention or reduction in skin irritation caused by a skin irritating detergent or detergent containing composition is achieved by incorporating in the detergent composition a protective agent having the formula L N n where R is the carboxyl free residue of an aromatic, cycloaliphatic or aralkyl di-, tri, or tetra-carboxylic acid or the carboxyl free residue of the unsaturated polycarboxylic acid product of the polymerization of two to four molecules of a monomeric ethylenically unsaturated C to C fatty acid or the hydrogenated derivative of said unsaturated polycarboxylic acid product; R is hydrogen, hydroxyl, C -C alkyl or C C -alkyl substituted with hydroxyl or amino;

R" and R' are hydrogen or C -C alkyl;

m is 0, l or 2;

nis 1,2,3or4;

n+mis 2,3or4;

M is H or a cation;

X is oxygen or nitrogen;

q is 0 when X is oxygen and q is 1 when X is nitrogen.-

The protective agent should be soluble or colloidally dispersible in an aqueous phase, compatible with the detergent or detergent composition and stable in aqueous media. The term dispersible is meant to define colloidal dispersibility of the protective agent in concentrations in which the protective agent is employed in actual use.

In accordance with the present invention, it has been discovered that skin irritation and other more severe forms. of dermatitis caused by contact with chemicals, particularly detergents, can be reduced or eliminated by contacting the skin with a protective agent as defined above. It has also been found that this reduction of skin irritation can be achieved by applying the protective agent to the skin prior to contact with the irri- Evidence, such as electrophoretic studies of mixtures of soluble proteins and protective agent, indicates that some form of interaction occurs between protein and the protective agent. Although the complex formed between protein molecules and the protective agent can beisolated by the indicated electrophoresis, the specific nature of the complex has not yet been established. Thus, it is postulated that an interaction occurs between the protein keratin layer of the skin and the protective agent. It is presumed that both adsorption and some form of chemical interaction are involved. It is further theorized that a cyclic structure in the protec tive agent can aid in the adsorption of the protective agent onto the keratin layer of the skin and that the protective agent interacts with the protein molecules of the keratin layer. It is believed that the protective agents are capable of and do interact with different protein molecules of the skin. The irritation of the skin by the action of a detergent or other irritant is believed to be caused by the penetration of the detergent into the skin, causing separation and/or degradation of the protein molecules of the keratin layer, thereby exposing the living cells of the skin to the detergent and, more significantly, exposing these cells to other more irritating compounds associated with the detergent. The damage to the cells caused by the contact is believed to result in irritation, inflammation, and dermatitis. The protective agents employed in the detergent compositions of the present invention are believed to counteract this breakdown by providing additional bridges between the protein molecules of the-keratin layer, which maintain the integrity of the skin surface thereby preventing the penetration of 'the detergent molecules through the keratin layer into the living tissue. It is to be understood, however, that we do not wish to be bound by the foregoing explanation of the activity of the protective agents of the present invention, and that such explanation is only set forth for a better understanding of the present invention.

The protective agents should be compatible with the detergent and should be of the type capable of existing in the aqueous phase, i.e., without irreversibly reacting with the water.

The protective agents of this invention can be obtained by methods of synthesis known in the art, such as are disclosed in US. Pat. No. 2,889,334 and U.S. Pat. No. 2,987,522, and U.S. Pat. No. 3,251,852, the

disclosure of which patents is incorporated by reference. Such methods may involve the reaction of a polycarboxylic acid with a 1,2-diamino alkane, a lhydroxy-2-amino alkane, a l amino-2-hydroxy alkane, an N-mono-substituted l,2-diamino alkane, 01,8 alkanol amine and an aliphatic a,,B-diamine. Alternatively, in place of the polycarboxylic acid the acid halide, e.g. acid chloride, maybe used. As non-limiting examples of polycarboxylic acids which may be used in the preparation of the protective agents of this invention there are included phthalic acid, isophthalic acid, terephthalic acid, trimesic acid, l,4-cyclohexane dicarboxylic acid, l,3-cyclohexane dicarboxylic acid, l,2- cyclohexane dicarboxylic acid, l,4-cyclohex 2-ene dicarboxylic acid, l,4-cyclohex--ene dicarboxylic acid, l,4-cyclohex-1-ene dicarboxylic acid, 1,4-cyclohex- 3-ene dicarboxylic acid, 1,3-cyclohex-2-ene dicarboxylic acid, l,3-cyclohex-3-ene dicarboxylic acid, l,3- cyclo-hex-5-ene dicarboxylic acid, l,2,4-cyclohexane tricarboxylic acid, 1,3,5-cyclohexane tricarboxylic acid, l,2,6-cyclohexane tricarboxylic acid, l,2,4- benzene tricarboxylic acid, o-benzene diacetic acid, pbenzene diacetic acid, m-benzene diacetic acid, 1,2- cyclohexane diacetic acid, l,3-cyclohexane diacetic acid, l,4-cyclohexane diacetic acid, 1,3,5-benzene triacetic acid, 1,3,5-cyclohexane triacetic acid, pyromellitic anhydride, pyromellitic acid, l,2,4,5-cyclohexane tetracarboxylic acid, l,2,4,5-cyclohexene tetracarboxylic acid and unsaturataed polycarboxylic acid products of the polymerization of two to four molecules of a monomeric ethylenically unsaturated C to C fatty acid or the hydrogenated derivatives of said unsaturated polycarboxylic acid products.

The starting materials comprising polymerized unsaturated polycarboxylic acids are obtained by polymerizing two to four molecules of ethylenically unsaturated C to C fatty acid to give products containing two to four carboxyl groups comprising the dimer, trimer, tetramer or mixtures thereof, possibly containing some of the starting fatty acid in unpolymerized form. The starting ethylenically unsaturated acid can be monoor polyunsaturated. Preferred unsaturated polycarboxylic acid products are obtained from linoleic acid. The

- sometimes preferred, especially where color is impor- HzCI I l ICH Ht t t t...

H2C -l I I I- CHZ mt s & JJH.

tant inasmuch as the saturated derivatives are often of a better, i.e., lighter, color than the corresponding unsaturated material.

Typical of the commercially available unsaturated polycarboxylic acid products useful in this invention are Empol Dimer Acids marketed by Emery Industries Inc. Literature supplied by Emery Industries Inc. indicates that reactions at the carboxyl group of Empol Dimer Acids aretypical of aliphatic carboxylic acids. Indeed, this has been found to be true. Thus, the conversion of the carboxyl group to the other groups mentioned herein is analogous to conversions used to prepare the corresponding derivatives of other carboxylic acids.

A number of patents teach methods of preparing the unsaturated polycarboxylic acid products which are useful in preparing the protective agents of this invention. Among these patents are US. Pat. Nos. 2,482,761, 2,793,219, and 3,157,681, the disclosure of which patents is incorporated herein by reference.

Examples of l,2-diamino alkanes include ethylene diamine, l,2-butane diamine, 1,2-propane diamine, l,2-pentane diamine and 1,2-hexanediamine.

Examples of l-hydroxy-2-amino alkanes include 1- hydroxy-2-amino propane, ethanol amine, l-hydroxy- 2-amino butane, l-hydroxy-Z-amino pentane and lhydroxy-2-amino hexane.

Examples of l-amino-Z-hydroxy alkanes include 1- amino-2-hydroxypropane, 1-amino-2-hydroxy butane, 1-amino-2-hydroxy pentane, and 1-amino-2-hydroxy hexane.

Examples of N-mono substituted 1,2-diamino alkanes include N-methyl ethylene diamine, N-ethyl ethylene diamine, N-propyl ethylene diamine, N-butyl ethylene diamine, hydroxy ethyl ethylene diamine, hy-

droxy propyl ethylene diamine, hydroxy butyl ethylene diamine, amino ethyl ethylene diamine, amino propyl ethylene diamine and amino butyl ethylene diamine.

The protective agents of this invention include but i are not limited to oiii-crr orrromoifor CH- H II! II Continued W I1I-CHR [D]( J H2 L \N 2 14 H2o( OOH2 H20 o-Q-h JJH:

(15) RHC() O CHR" H2d c b 5H2 N/ \N (16) HzC O (|)-CH2 ri -He t -o ('JH-R 17 R' EE E a i 7 East )f CH H fill! RI! (l8) OCH2 [D] /JJHz 19 |"o 0H-R" [D]- /CH2 (2o) 0 oH-R" [D]-C\ oHR'" (21); OCH2 [T][(]J\ (:H;

E MOOO-[T]O CH2 2 R (3) COOM H2C|] N H2C C- o N-R' CH2CH2 24) III.

' 1TICH2 MOOC[D]C CH2 L N 25) 3Hr M00o- D] o CH2 L N (26) l-( )oHr MOOC[T]-C CH2 Where [D] is the carboxyl free residue of dimerized 1ino1eic acid.

Where [D] is the carboxyl free residue of dimerized linoleic acid and R" is CH2, CH2CH3 or CH2CH2CH3.

Where [D] is the carboxyl free residue of dimarized linoleic acid and R and R are -CHs, OHzCHa or CHzCHzCHa.

Where [T] is the carboxyl free residue of trimerized linoleic acid.

Where [T] is the carboxvl free residue of trimerized linoleic acid; R 7

2-CH2NH2; and M is H, Na, K or the triethanolamine cation.

Where R is H, CH3, CH2CH3, CH2CH2OH, or CH2OH2NH2; and M is H, Na, K or the triethanolamine cation.

Where [D] is the carboxyl free residue of dimerized linoleic acid, and

M is H, N a, K or the triethanolamine cation.

Where [T] is the carboxyl free residue of trimerized linoleic acid; and

M is H, Na, K or the triethanolamine cation.

The protective agents described herein above can be employed in combination with any detergent that is anionic, cationic, nonionic or amphoteric in nature. It will be apparent, however, that the protective agent should be compatible with the detergent to avoid precipitation of both detergent and agent. The reduction of skin irritation will be observable in all compatible combinations, although the extent of the anti-irritant effect will differ with the various protective agents discussed, as well as with the detergent. Since some of the detergents, particularly nonionic detergents, areby themselves relatively nonirritating, the described protective agent is less useful, although the protective effect of the agent can be established when such detergents, which at normally used concentrations cause little or no skin irritation, are tested at high concentrations and/or longer periods of contact with the skin.

The anti-irritation effect of the protective agent is exhibited over a wide range of proportions of agent to detergent (e.g. 0.00521 to 10:1 by weight) as indicated above. However, optimum results are generally obtained when the ratio of detergent to protective agent is in the range of 3:1 to 1:3 by weight. This preferred range is applicable regardless of whether the detergent C non-soap anionic detergents with which the described protective agents are suitably employed include alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates, alkyl phenyl polyoxyalkylene sulfonates, alkyl glyceryl ether sulfonates, alkyl monoglyceride sulfates, alkyl monoglyceride sulfonates, alkyl polyoxyethylene ether sulfates, acyl sarcosinates, acyl esters of isothionates, acyl-N-methyl taurides, dialkyl esters of sulfosuccinic acid, and mixtures thereof. In these non-soap detergents, the alkyl or acyl radicals contain from nine to 20 carbon atoms. As in the soaps, these detergents are employed in the form of sodium, potassium, ammonium, and alkylolammonium salts, as well as similar water-soluble salts. Specific examples include sodium lauryl sulfate, potassium-N-methyl lauroyl tauride, triethanol ammonium dodecyl sulfonate, potassium polyoxypropylene benzene sulfonate, sodium lauryl sulfonate, dioctyl ester of sodium sulfosuccinic acid, sodium salt of lauryl polyoxyethylene sulfate, and sodium salt of tridecylether polyoxyethylene sulfate.

The cationic detergents which can be reduced in their skin irritation by the addition of the protective agents of the present invention include, in particular, quaternary ammonium salts which contain at least one alkyl group having 12 to 20 carbon atoms. Although the halide ions are the mostcommon anions, the anion can be acetate, phosphate, sulfate, nitrite, or the like. Specific cationic detergents include distearyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, stearyl trimethyl ammonium chloride, coco dimethyl benzyl ammonium chloride, dicoco dimethyl ammonium chloride, cetyl pyridinium chloride, cetyl trimethyl ammonium bromide, stearyl amine salts that are soluble in water such as stearyl amine acetate and stearyl amine hydrochloride, stearyl dimethyl amine hydrochloride, distearyl amine hydrochloride, alkyl phenoxyethyoxyethyl dimethyl ammonium chloride, decylpyridinium bromide, pyridinium chloride derivative of the acetyl amino ethyl esters of lauric acid, lauryl trimethyl ammonium chloride, decyl amine acetate, lauryl dimethyl ethyl ammonium chloride, the lactic acid and citric acid and other acid salts of stearyll-amido-imidazoline with methyl chloride, benzyl chloride, chloroacetic acid and similar compounds, mixtures of the foregoing, and the like.

fects of the addition of the protective agent are less pronounced since nonionic detergents are inherently hot as irritating as the above-described detergents. Nonionic detergents include, in particular, the alkylene oxide ethers of phenols, fatty alcohols, and alkyl mercaptans, the alkylene oxide esters of fatty acids, the alkylene oxide ethers of fatty acid amides, the condensation products of ethylene oxide with partial fatty acid esters, and mixtures thereof. The polyoxyalkylene chain in such detergents can contain from five to 30 alkylene oxide units in which each alkylene unit has from two to three carbon atoms. Specific examples of nonionic detergents include nonyl phenol polyoxyethylene ether, tridecyl alcohol polyoxyethylene ether, dodecyl mercaptan polyoxyethylene thioether, the lauric ester of polyethylene glycol, the lauric ester of methoxy polyethylene glycol, the lauric ester of sorbitan polyoxyethylene glycol, the lauric ester of sorbitan polyoxyethylene ether, and mixtures thereof.

The protective agents of the present invention are particularly effective in reducing the irritationcaused by such anionic detergents as the alkyl sulfates and sulfonates and the alkyl benzene sulfates and sulfonates, and by such cationic detergents as the described fatty alkyl-containing quaternary ammonium compounds.

Many of the detergents described hereinabove are employed in their commercial application in combination with builders or other additives, depending on the intended commercial utilityof the detergent. The presence of such additives does not affect the ability of the protective agent to counteract the skin irritation caused by the detergent. As indicated above, it is believed that the skin irritation is caused by the action of the detergent on the skin in causing the keratin of the skin to break down. Although the detergent itself may not be extremely irritating, it allows other materials employed in combination with the detergent which are highly irritating to come in contact with the living tissue of the skin, even though in the absence of the detergent such materials are non-irritating in not being able to break down the keratin of the skin. The protective agents of the present invention are, therefore, capable of protecting the skin against skin irritation caused by such additives. Builders employed in commerical detergent formulations are generally alkali salts of weak inorganic acids used alone or in admixtures, such as alkali metal, ammonium or substituted ammonium salts of carbonates, borates, phosphates, polyphosphates, bicarbonates, and silicates. Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium monoand diorthophosphate, sodium metasilicate, and mixtures thereof.

The built detergent compositions of the present invention can, furthermore, contain other adjuvants normally employed in detergent compositions such as perfumes, anti-tarnishing agents, anti-redeposition agents, bacteriostatic agents, dyes, fluorescers, fabric softeners, oxygen or chlorine bleaches, suids builds, suds debased on a scale of l to 10, in which the numbers have the meanings given in Table 1 below. i

TABLE I pressors, sequestrants, and the like. The inorganic Grade or builders or the combination of the builders and the ad- Rating Gross Reaction Skin Damage juvants described can constitute up to 80% of the built detergent composition, the remainder of the built de- 1 3353533 5 3? bleedmg; 5331;255: tergent composition being the detergent and the proin most instances {active agent 10 2 lSfleeveedriencracking; moderate do The detergent compositions of the present invention 3 Severe iracking; Slight to Severe include laundry detergents, kitchen detergents, shammoderate bleeding poos, industrial detergents, and the like. The use of the g g jfi fg i z Mgg protective agent of the present invention does not af- 6 Severe scaling do. fect the effective concentrations of the detergent, and 5 7 p Slight hence concentrations of detergents heretofore em- 3 gif lli and moderate Slight ployed are also applicable in the modified compositions edema of the present invention. fig g and edma flfig The use of the protective agent is, however, not lim- I ited to uhbuht detergent e h h additive Despite the fact that this exposure test is conducted can be employed In h eorhposmohs whleh a deter using extremely dilute solutions, it is an exaggerated gem of the type deschbed employed In the presence test as compared to human exposure; although it has of olher mtterials which l Cause ifritalion Such beeh established (see Canadian Pat. No. 639,398) that m Particular m lubneants .eohtammg .mergahle the test correlates extremely well with the skin irritasalts, a particular example of WhlCh are cutting fluids. tion effect Observed on human skin h irritant can e inorganic i W or i In In preparing the test solution, a 100 g concentrate is of the foregomg eXplahahOh.thlS not Surpnsmg first prepared which is then employed in the test solusince the protection derived from the protective agent tion in 1 percent by volume Concentrations In the is based on the interaction of such with the keratin preparation of the homogeneous concentrate which layer of the skin and not on interaction with the irritant. was readily dilutahle the following additional ingredi Because of this interaction, it is, furthermore, unnecesem was added as required; Igepal CA 63O, a teary to eemblhe the Protect? agent h the cially available nonionic wetting agent of octylphenoxin order to achieve the protection of the skin. Thus, the yholy (oxyethylene) ethanoh In general the detergent proteehve, agent, a be apphed to the 5km prlor to and the protective agent are each employed in the data Contact wlth. h "m and agamst illustrated below in a concentration of 15 weight persubseque? F' h period of cent based on the described 100 g concentrate. Where In establishing the mltatmahd the Protect? effect a built detergent is employed, the amount of detergent of the protective agent, the skin s contacted by l h f is accordingly adjusted to take into consideration the sion or other means with a solution containing the lrrrlower active detergent concentration tant with and without the protective agent under stan- 40 dardized conditions more specifically described below. EXAMPLES l-9 The e e test employed In e data preseneed The following Examples illustrate the effect of the below f ammal tmmerslqn F usmgfemale, albmo protective agents of the present invention on reducing guinea p The ammalt welghmg about 300 to 325 gt skin irritation caused by detergents. is immersed up to the thoracic region in the test solu- I h f the Examples, the above-described test {ion at C for hours P y on 3 Successive y was conducted with control detergent compositions Each animal is thOI'OUghly rinsed and dried after each (Examples 1 and and the protective agent containimmersion. 3 days after the last immersions, the skin of ing composition of this invention (Examples 3-9). The each animal is examined for g os g and grades degree of irritation was measured and is tabulated in are assigned which represent the degree of damage to Table II below in which the substituents of the protecthe skin. In general, three animals are tested simulta-. tive agents correspond to those set forth in formula I neously in the same solution. The grading system is above.

" TABLE II Example Number R R R" R' m n q X Detergent Rating '1 0 SLS 3 2 0- ABS 4 3 [D] CH, CH H H 0 2 l N SLS s 4 to ciT, cH H H o 2 1' N ABS s 5+ 0* H H H 0 2 l N SLS '9 6+ [0* H H 0 2 1 N ABS 9 7+ [D] H-CH- 0 2 0 0 81.8 7

TABLE I] Continued Example Number R R R" R' m n q X Detergent Rating 8 [D] H H 2 0 O SLS 8 9 [D] H H H O 2 l N SLS 9 lgepal CA 630 added [D] is the carboxyl free residue of dimerized linoleic acid (Empol l0l4) [D'| is the carboxyl free residue of the hydrogenated dimerized linoleic acid (Empol l0l0) SLS is sodium lauryl sulfate ABS is alkyl benzene sulfonate having the formula I SOrNa CHR HR/II in which R is the carboxyl-free residue of an aromatic, cycloaliphatic or aralkyl di-, trior tetra-carboxylic acid in which the aromatic, cycloaliphatic or aralkyl group is a C cyclic group and in which the carboxyl groups are attached to the C cyclic group, directly or through -CH radicals; the carboxyl-free residue of the unsaturated polycarboxylic acid prodnot obtained by the polymerization of two to four molecules of a monomeric ethylenically unsaturated C to C fatty acid; or the carboxyl-free residue of the hydrogenated derivative of said unsaturated polycar'boxylic acid product;

. R is hydrogen, hydroxyl, C C -a1kyl, or C -C alkyl substituted with hydroxyl or amine;

R and R are hydrogen or C C -alkyl;

X is oxygen or nitrogen;

M is H, or a cation;

m is 0, l or 2;

nis 1,2, 3, or 4;

q is 0 when X is oxygen and q is 1 when X is nitrogen; said detergent composition enhibiting reduced skin irritation relative to the said detergent composition absent the protective agent.

2. The detergent composition of claim 1 wherein R is the carboxyl-free residue of a cycloaliphatic dicarboxylic acid selected from the group consisting of cyclohexane dicarboxylic acids, cyclohexene dicarboxylic acids and cyclohexane diacetic acids, wherein the cyclohexene dicarboxylic acid is 1,4-cyclohex 2-ene dicarboxylic' acid, 1,4-cyclohex-5-ene dicarboxylic acid, 1,4-cyclohex-l-ene dicarboxylic acid, 1,4- cyclohex-3-ene dicarboxylic acid, 1,3-cyclohe-x-2-ene dicarboxylic acid, 1,3-cyclohex-3-ene dicarboxylic acid or l,3-cyclohex-5-ene dicarboxylic acid.

3. The detergent composition of claim 1 wherein R is the carboxyl-free residue of an aralkyl dicarboxylic acid selected from the group consisting of o-benzene diacetic acid, m-benzene diacetic acid and p-benzene diacetic acid.

4. The detergent composition of claim 1 wherein the said protective agent is employed in an amount of from 0.005 to 10 parts by weight per part by weight of the said detergent. v

5. The detergent composition of claim 1 wherein R is the carboxyl free residue of the unsaturated polycarboxylic acid product obtained by the polymerization of two to four molecules of a monomeric ethylenically unsaturated C to C fatty acid.

6. The detergent composition of claim 5 wherein R -is the carboxyl free residue of dimerized linoleic acid.

7. The detergent composition of claim 1 wherein R is the carboxyl free residue of the hydrogenated derivative of the unsaturated polycarboxylic acid obtained by the polymerization of 2 to 4 molecules of a monomeric ethylenically unsaturated C to C fatty acid.

8. The detergent composition of claim 1 wherein R is the carboxyl free residue of a benzene dicarboxylic acid.

9. The detergent composition of claim 1 wherein said detergent is an anionic detergent.

10. The detergent composition of claim 1 wherein said detergent is a cationic detergent.

11. The detergent composition of claim 1 wherein said detergent is a nonionic detergent. g

12. The detergent composition of claim 1 wherein said detergent is an amphoteric detergent.

13. The composition of claim 1 wherein the detergent composition contains from 10 to percent by weight of the composition of inorganic water soluble detergent builders.

14. The detergent composition of claim 2 wherein R is -CH -CH OH, R" and R' are hydrogen;

m is 0; i

n is 2;

q is l; and

X is nitrogen.

15. The detergent composition of claim 2 wherein R" and R' are hydrogen;

m is 0;

n is 2;

q is O; and

X is oxygen.

16.' The detergent composition of claim 2 wherein R" -is hydrogen;

m is 0;

n is 2;

q is 0; and

X is oxygen.

17. The detergent composition of claim 7 wherein R is the carboxyl free residue of the hydrogenated derivative of dimerized linoleic acid.

18. The detergent composition of claim 17 wherein R is hydrogen;

R" and R are hydrogen;

m is

n is 2;

q is l; and

X is nitrogen.

19. The detergent composition of claim 8 wherein the said carboxyl free residue of a benzene dicarboxylic acid is the carboxyl free residue of isophthalic. acid.

20. The detergent composition of claim 19 wherein R is hydrogen;

R" and R' are hydrogen;

m is 0;

n is 2;

q is l; and

X is nitrogen.

22. The method of reducing skin irritation caused by contacting the skin with a skin irritating detergent or detergent composition comprising contacting the skin, prior to or concurrently with contact with the irritating detergent, or detergent composition, with a protective agent having the formula urated C to C fatty acid; or the carboxyl-free residue of the hydrogenated derivative of said unsaturated polycarboxylic acid product; R is hydrogen, hydroxyl, C 'C -alkyl, C,C -alkyl substituted with hydroxyl or amine; R" and R" are hydrogen or C -C -alkyl; m is 0,- 1 or 2; n is l, 2, 3, or 4; n+mis2;3,or4; X is oxygen or nitrogen; M is H or a cation; and q is 0 when X is oxygen and q is 1 when X is nitrogen. 23. The method of claim 22 in which the skin is contacted concurrently with said skin irritating detergent or detergent composition and said protective agent.

24. The method of claim 22 in which the skin is contacted with said protective agent prior to contact with said skin irritating detergent or detergent composition. 

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A SKIN IRRITATING DETERGENT AND A SKIN IRRITATION REDUCING EFFECTIVE AMOUNT OF A COMPATIBLE PROTECTIVE AGENT HAVING THE FORMULA
 2. The detergent composition of claim 1 wherein R is the carboxyl-free residue of a cycloaliphatic dicarboxylic acid selected from the group consisting of cyclohexane dicarboxylic acids, cyclohexene dicarboxylic acids and cyclohexane diacetic acids, wherein the cyclohexene dicarboxylic acid is 1,4-cyclohex 2-ene dicarboxylic acid, 1,4-cyclohex-5-ene dicarboxylic acid, 1, 4-cyclohex-1-ene dicarboxylic acid, 1,4-cyclohex-3-ene dicarboxylic acid, 1,3-cyclohex-2-ene dicarboxylic acid, 1,3-cyclohex-3-ene dicarboxylic acid or 1,3-cyclohex-5-ene dicarboxylic acid.
 3. The detergent composition of claim 1 wherein R is the carboxyl-free residue of an aralkyl dicarboxylic acid selected from the group consisting of o-benzene diacetic acid, m-benzene diacetic acid and p-benzene diacetic acid.
 4. The detergent composition of claim 1 wherein the said protective agent is employed in an amount of from 0.005 to 10 parts by weight per part by weight of the said detergent.
 5. The detergent composition of claim 1 wherein R is the carboxyl free residue of the unsaturated polycarboxylic acid product obtained by the polymerization of two to four molecules of a monomeric ethylenically unsaturated C12 to C26 fatty acid.
 6. The detergent composition of claim 5 wherein R is the carboxyl free residue of dimerized linoleic acid.
 7. The detergent composition of claim 1 wherein R is the carboxyl free residue of the hydrogenated derivative of the unsaturated polycarboxylic acid obtained by the polymerization of 2 to 4 molecules of a monomeric ethylenically unsaturated C12 to C26 fatty acid.
 8. The detergent composition of claim 1 wherein R is the carboxyl free residue of a benzene dicarboxylic acid.
 9. The detergent composition of claim 1 wherein said detergent is an anionic detergent.
 10. The detergent compositIon of claim 1 wherein said detergent is a cationic detergent.
 11. The detergent composition of claim 1 wherein said detergent is a nonionic detergent.
 12. The detergent composition of claim 1 wherein said detergent is an amphoteric detergent.
 13. The composition of claim 1 wherein the detergent composition contains from 10 to 80 percent by weight of the composition of inorganic water soluble detergent builders.
 14. The detergent composition of claim 2 wherein R'' is -CH2-CH2-OH, R'''' and R'''''' are hydrogen; m is 0; n is 2; q is 1; and X is nitrogen.
 15. The detergent composition of claim 2 wherein R'''' and R'''''' are hydrogen; m is 0; n is 2; q is 0; and X is oxygen.
 16. The detergent composition of claim 2 wherein R'''' is hydrogen; R'''''' is -CH2-CH3; m is 0; n is 2; q is 0; and X is oxygen.
 17. The detergent composition of claim 7 wherein R is the carboxyl free residue of the hydrogenated derivative of dimerized linoleic acid.
 18. The detergent composition of claim 17 wherein R'' is hydrogen; R'''' and R'''''' are hydrogen; m is 0; n is 2; q is 1; and X is nitrogen.
 19. The detergent composition of claim 8 wherein the said carboxyl free residue of a benzene dicarboxylic acid is the carboxyl free residue of isophthalic acid.
 20. The detergent composition of claim 19 wherein R'' is hydrogen; R'''' and R'''''' are hydrogen; m is 0; n is 2; q is 1; and X is nitrogen.
 21. The detergent composition of claim 19 wherein R'' is -CH2-CH2-OH; R'''' and R'''''' are hydrogen; m is 0; n is 2; q is 1; and X is nitrogen.
 22. The method of reducing skin irritation caused by contacting the skin with a skin irritating detergent or detergent composition comprising contacting the skin, prior to or concurrently with contact with the irritating detergent, or detergent composition, with a protective agent having the formula
 23. The method of claim 22 in which the skin is contacted concurrently with said skin irritating detergent or detergent composition and said protective agent.
 24. The method of claim 22 in which the skin is contacted with said protective agent prior to contact with said skin irritating detergent or detergent composition. 